Electrical barrier layers

ABSTRACT

An electrical connection structure includes a variable-composition nickel alloy layer with a minor constituent selected from a group consisting of boron, carbon, and tungsten, wherein at least over a portion of a conductive substrate, the concentration of the minor constituent varies throughout the variable-composition nickel alloy layer in a direction from the bottom surface of the variable-composition nickel alloy layer to the top surface of the variable-composition nickel alloy layer.

BACKGROUND OF THE DISCLOSURE

Barrier layers can be used in myriad electrical connections in a varietyof electrical applications. For example, a barrier layer can be used insemiconductor applications to prevent diffusion of the materialsadjacent the barrier layer. For example, a barrier layer can be used toprevent diffusion between a substrate layer and an adhesion layer.Barrier layers can also be used to promote the adhesion (i.e., thewetting characteristic) between two or more materials, such as between asubstrate layer and an adhesion layer. Barrier layers can be also usedin, for example without limitation, semiconductor chip structures,packaging, flat panel applications, and magnetics.

In order to minimize the overall size of the electronic structure inwhich the barrier layer is used (e.g., an interconnect structure) and toreduce manufacturing costs, it would be beneficial to incorporatebarrier layers that are thinner than traditional barrier layers yetretain the functionality of the barrier layer, such as preventingdiffusion of the layers adjacent the barrier and providing adhesion.

SUMMARY OF THE DISCLOSURE

One aspect of the disclosure is a conductive pad adapted to create anelectrical connection, comprising a conductive substrate, avariable-composition nickel alloy layer disposed above the conductivesubstrate, and a conductive layer disposed above thevariable-composition nickel alloy layer.

In some embodiments the variable-composition nickel alloy layer has avariable nickel concentration within the layer. The nickel concentrationcan vary between about 80% and 100% within the layer.

In some embodiments the variable-composition nickel alloy layer has avariable boron concentration within the layer. The boron concentrationcan vary between about 0% and about 5% within the layer, Thenickel-alloy layer can have first and second surfaces, the first surfacebeing closer to the substrate than the second surface, and wherein theconcentration of boron is higher at the first surface than the boronconcentration at the second surface.

In some embodiments the variable-composition nickel alloy layercomprises a minor constituent whose concentration varies linearlythroughout the alloy layer.

In some embodiments the variable-composition nickel alloy layercomprises a minor constituent whose concentration varies non-linearlythroughout the alloy layer.

In some embodiments the variable-composition nickel alloy has a variablecarbon concentration within the layer. The carbon concentration can varybetween about 0% and about 5% within the layer.

In some embodiments the pad further comprises a nickel layer disposed onthe conductive substrate, wherein the variable-composition nickel alloylayer is disposed on the nickel layer. The conductive layer can bedisposed on the variable-composition nickel alloy layer. A second nickellayer can be disposed on the variable-composition nickel alloy layer,wherein the conductive layer is disposed on the second nickel layer. Insome embodiments the combined depths of the nickel layer,variable-composition nickel alloy layer, and second nickel layer isbetween about 0.01 and 1.5 microns. The nickel layer can have athickness of between about 5 nm and about 50 nm.

In some embodiments the pad further comprises a nickel layer disposed onthe variable-composition nickel alloy layer. The variable-compositionnickel alloy layer can be disposed on the conductive substrate. Theconductive layer can be disposed on the nickel layer. The pad canfurther comprise a second variable-composition nickel alloy layerdisposed on the nickel layer. The combined thicknesses of thevariable-composition nickel alloy layer, nickel layer, and secondvariable-composition nickel alloy layer can be between about 0.01 andabout 1.5 microns.

In some embodiments a thickness between the conductive substrate and theconductive layer is between about 0.01 and about 1.5 microns.

In some embodiments a thickness of the nickel alloy layer is betweenabout 20 and about 200 nm.

In some embodiments the conductive layer is a solder material.

One aspect of the disclosure is a method of preparing a conductive padas an electrical connection, comprising providing a conductivesubstrate, plating a variable-composition nickel alloy layer above theconductive substrate, and plating a conductive layer above thevariable-composition nickel alloy layer.

In some embodiments plating a variable-composition nickel alloy layercomprises plating the layer with a varying concentration of nickelwithin the layer.

In some embodiments plating a variable-composition nickel alloy layercomprises plating the layer with a varying concentration of boron withinthe layer. Plating the layer with a varying concentration of boronwithin the layer can comprise plating the layer such that the boronvaries between a concentration of about 0% and about 5% within thelayer.

In some embodiments plating the variable-composition nickel alloy layercomprises plating a higher concentration of a minor constituent closerto the conductive substrate than the conductive layer. The plating stepcan comprise plating a higher concentration of boron closer to theconductive substrate than the conductive layer.

In some embodiments plating a variable-composition nickel alloy layercomprises plating the layer with a varying concentration of carbonwithin the layer, such as between about 0% and about 5% within thelayer.

In some embodiments plating a variable-composition nickel alloy layercomprises exposing the nickel alloy to at least one of oxygen andnitrogen gas. Exposing the nickel alloy to at least one of oxygen andnitrogen gas can comprise modulating the amount of nitrogen gas to whichthe alloy is exposed to vary the concentration of nickel that isdeposited. Exposing the nickel alloy to at least one of oxygen andnitrogen gas comprises modulating the amount of oxygen gas to which thealloy is exposed to vary the concentration of nickel that is deposited.Exposing the nickel alloy to at least one of oxygen and nitrogen gas cancomprise modulating the amount of nitrogen gas to which the alloy isexposed to vary the concentration of boron that is deposited. Exposingthe nickel alloy to at least one of oxygen and nitrogen gas comprisesmodulating the amount of oxygen gas to which the alloy is exposed tovary the concentration of boron that is deposited.

In some embodiments the method further comprises plating a nickel layerabove the conductive substrate. Plating a nickel layer can compriseplating a nickel layer on the conductive substrate, wherein thevariable-composition nickel alloy layer is plated on the nickel layer.The method can also include plating a second nickel layer on thevariable-composition nickel alloy layer. Plating the conductive layercan comprise plating a gold layer on the second nickel layer. Platingthe nickel layer can comprise plating the nickel layer on thevariable-composition nickel alloy layer. A second variable-compositionnickel alloy layer can be plated on the nickel layer. Plating theconductive layer can comprise plating the conductive layer on the secondvariable-composition nickel alloy layer. Plating the nickel layer cancomprise flash plating the nickel layer to a thickness of about 5 nm toabout 50 nm.

In some embodiments the method further comprises creating a thicknessbetween the conductive substrate and the conductive layer that is about0.01 microns to about 1.5 microns.

In some embodiments plating a variable-composition nickel alloy layercomprises plating a variable-composition nickel alloy layer that isabout 20 to about 200 nm thick.

One aspect of the disclosure is a conductive pad adapted to create anelectrical connection, comprising a conducting substrate, a nickel layerdisposed on the conducting substrate, a nickel alloy layer disposed onthe nickel layer, and a conductive layer disposed above the nickel alloylayer.

In some embodiments a second nickel layer is disposed on the nickelalloy layer and under the conductive layer. The conductive layer can bedisposed on the second nickel layer. The combined depths of the nickellayer, nickel alloy layer, and second nickel layer can be between about0.01 and about 1.5 microns.

In some embodiments the nickel alloy layer is a nickel-boron alloy. Theboron can be present in the amount from about 0% to about 5% by weight.

In some embodiments the nickel alloy layer is a nickel-carbon alloy. Thecarbon can be present in the amount from about 0% to about 5% by weight.

In some embodiments the nickel layer has a thickness of about 5 to about50 nm.

In some embodiments the conducting substrate is a copper layer.

In some embodiments the nickel alloy layer is a variable-compositionnickel alloy layer. The nickel alloy layer can have a variable nickelconcentration within the layer. The nickel alloy layer can have avariable boron concentration within the layer. The nickel alloy layercan have a variable carbon concentration within the layer.

In some embodiments the nickel alloy layer has a thickness of betweenabout 20 and about 200 nm.

In some embodiments the conductive layer is a solder material.

One aspect of the disclosure is a conductive pad adapted to create anelectrical connection, comprising a conducting substrate, a nickel alloylayer disposed on the conducting substrate, a nickel layer disposed onthe nickel alloy layer, and a conductive layer disposed above the nickellayer. The pad can also include a second nickel alloy layer disposed onthe nickel layer. The conductive layer can be disposed on the secondnickel alloy. The combined thickness of the nickel alloy layer, nickellayer, and second nickel alloy layer can be between about 0.01 and about1.5 microns.

In some embodiments the nickel alloy layer is a nickel-boron alloy. Theboron can be present in the amount from about 0% to about 5% by weight.

In some embodiments the nickel alloy layer is a nickel-carbon alloy. Thecarbon can be present in the amount from about 0% to about 5% by weight.

In some embodiments the nickel layer has a thickness of about 5 nm toahout 50 nm.

In some embodiments the conducting substrate is a copper layer.

In some embodiments the nickel alloy layer is a variable-compositionnickel alloy layer. The nickel alloy layer can have a variable nickelconcentration within the layer. The nickel alloy layer can have avariable boron concentration within the layer. The nickel alloy layercan have a variable carbon concentration within the layer.

In some embodiments the conductive layer is a solder material.

In some embodiments the nickel alloy layer has a thickness of about 20nm to about 200 nm.

One aspect of the disclosure is a conductive pad adapted to create anelectrical connection, comprising a copper substrate, a nickel layerdisposed on the conducting substrate, a nickel-boron layer disposed onthe nickel layer, and a conductive layer disposed above the nickellayer.

In some embodiments the nickel layer has a thickness of about 5 nm toabout 50 nm.

In some embodiments the nickel boron layer has a thickness of about 20nm to about 200 nm.

In some embodiments a distance between the copper substrate and theconductive layer is about 0.01 microns to about 1.5 microns.

INCORPORATION BY REFERENCE

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

A better understanding of the features and advantages of the presentdisclosure will be obtained by reference to the following detaileddescription that sets forth illustrative embodiments, in which theprinciples of the disclosure are utilized, and the accompanying drawingsof which:

FIGS. 1A and 1B illustrate exemplary prior art metal connectors that canbe used in semiconductor applications.

FIGS. 2A-2F illustrate a traditional exemplary method of manufacturingelectrical connections for semiconductor Chip packaging.

FIG. 3 illustrates a conventional prior art wire bond connector.

FIGS. 4A-5B illustrate exemplary connectors with laminated barrierlayers.

FIG. 6A illustrates an exemplary graded alloy barrier layer with avarying concentration of a minor constituent.

FIG. 6B illustrates a barrier layer with a first graded portion and asecond uniform portion.

FIG. 6C illustrates a barrier layer with a first graded portion and asecond uniform portion.

FIGS. 7A-7B illustrate an exemplary process of plating a connetor thatincludes depositing a barrier layer.

FIGS. 8A-8C illustrate an exemplary process of plating a wire bondincluding a barrier layer

FIGS. 9A-9D illustrate an exemplary process of plating exemplarysolderable structures.

FIGS. 10A-10B illustrate exemplary connector structures including abarrier layer.

FIGS. 11A-12 show scanning electron microscope images of exemplarybarrier layers.

DETAILED DESCRIPTION

The disclosure is related to electrical connections and their methods ofmanufacture. In particular, the disclosure describes barrier layers thatcan be incorporated into a wide variety of electrical connections. Forexample, the barrier layers can be used in any electrical connector insemiconductor applications, packaging applications, magnetic and flatpanel applications. Barriers layers described herein provide the benefitof being thinner than traditional barrier layers, yet still provide thebenefits of the barrier layer, such as preventing the diffusion ofmaterials adjacent the barrier layer, providing adequate adhesion ofmaterials adjacent the barrier layer, etc.

FIGS. 1A and 1B illustrate exemplary prior art metal connectors 11 thatcan be used in semiconductor applications. FIG. 1B highlights individuallayers in connectors 11. Connectors 11 include substrate 16, barrier 18,adhesion layer 20, and solder bump 22. Connectors 11 also includedielectric 14 and metal wiring 12.

FIGS. 2A-2F illustrate an exemplary traditional method of manufacturingelectrical connections, such as can be found in, for example withoutlimitation, semiconductor chip packaging. In FIG. 2A, substrate 32 isdeposited on dielectric 30. In FIG. 2B, passivation layer 36 is coatedon substrate 32 and dielectric 30, and polymeric material 38 isdeposited on passivation layer 36. In FIG. 2C, polymer 38 has beencured, lithographically patterned, and portions of polymer 38 andpassivation layer 36 have been removed by reactive ion etching (“RIE”)methods to expose a portion of substrate 32 underneath.

In FIG. 2D, the patterned surface is coated with a suitable barrierlayer 40 and seed layer 42. In FIG. 2E, resist 46 has been applied tothe surface and patterned, after which solder material 44 is depositedwithin the cavity defined by resist 46 and seed layer 42. As shown inFIG. 2F, after resist 46 has been stripped, and portions of barrier 40and seed layer 42 removed, the solder is reflowed to form a solder bumpas shown.

FIG. 3 illustrates a conventional prior art wire bond connector.Connector 50 includes dielectric 52, substrate 54, passivation layer 56,polymer 58, barrier 60, and conductor 62. In some conventionalembodiments the barrier layer is a titanium-tungsten layer, and theconductor is an aluminum copper alloy layer.

One aspect of the disclosure provides for laminated barrier layers, thatis, one or more discrete layers within the overall barrier structure.The laminated barrier layers include at least one alloy layer. FIG. 4Aillustrates an exemplary connector (or a portion of a connector) with alaminated barrier layer. Connector 200 includes substrate 202, barrier210, and conductive layer 208. Barrier 210 includes first barrier layer204 and second barrier layer 206. In one exemplary embodiment, firstbarrier layer 204 is a nickel layer, and second barrier layer 206 is anickel-boron alloy layer.

Boron in the nickel-boron alloy tends to increase the barrier layer'sability to resist corrosion in the substrate layer. As the amount ofboron increases, however, the interface between the substrate andbarrier tends to undesirably become more brittle. It is generally betterto make any boron containing alloy layers as thin as possible todecrease the brittleness of the substrate/barrier interface.Additionally, as in the embodiment in FIG. 4A, the very thin barrierlayer 204, which does not include boron, eliminates the presence ofboron at the substrate/barrier interface, thereby significantly reducingthe likelihood of cracks at the substrate/barrier interface.Additionally, keeping first barrier layer 204 very thin helps keep theoverall barrier layer very thin.

FIG. 4B illustrates an alternative embodiment of a connector. Connector220 includes substrate 222, barrier 225, and conductive layer 230.Laminated barrier layer 225 includes first layer 224, second layer 226,and third layer 228. In one exemplary embodiment, first layer 224 isnickel, second layer 226 is a nickel-boron alloy, and third layer 228 isnickel, forming a Ni/NiB/Ni laminated barrier layer. In some embodimentslayer 224 has a thickness between about 5 nm and about 50 nm. In someembodiments layer 226 has a thickness between about 20 nm about 200 nm.In some embodiments layer 228 has a thickness between about 3 nm about50 nm. Layer 228 can have a minimum thickness of about 3 nm because thelayer should have (in this embodiment) a continuous layer of materialwithout creating gaps in the layer, which produces “islands” in thelayer. When the thickness is below 3 nm, it can be difficult (dependingon the process used) to satisfactorily create a continuous layer ofmaterial without creating “islands.” The minimum acceptable thickness,however, will depend on the method of producing the layer, and 3 nm isillustrative and not intended to be limiting.

FIG. 5A illustrates an exemplary connector. Connector 240 includessubstrate 242, harrier layer 247, and conductive layer 248. Barrierlayer 247 includes first layer 244 and second layer 246. In oneexemplary embodiment, first layer 244 is a nickel-alloy, and secondlayer 246 is nickel, forming a NiB/Ni laminated. barrier layer.

FIG. 5B illustrates an exemplary connector. Connector 260 includessubstrate 262, barrier layer 272, and conductive layer 270. Barrierlayer 272 includes first layer 264, second layer 266, and third layer268. In one particular embodiment first layer 264 is a nickel-boronalloy, second layer 266 is a nickel layer, and third layer 268 is anickel alloy, providing a NiB/Ni/NiB laminated barrier layer. In someembodiments layer 264 has a thickness between about 20 nm and about 200nm. In some embodiments layer 266 has a thickness between about 5 nm andabout 50 nm. In some embodiments layer 268 has a thickness between about20 nm about 200 nm, and the same thickness considerations mentionedabove with respect to FIG. 4B can similarly apply to the embodiment inFIG. 5B.

The conductive layer, such as layer 208, layer 230, layer 248, and layer270, in FIGS. 4A-5B, respectively can be any suitable conductivematerial, such as, gold, silver, palladium, platinum, nickel, copper,copper particles, a solder material, solder paste, silver paste,conducting paste, and conducting adhesive.

The alloy layers can have a minor constituent present at a concentrationfrom about 1% to about 49% of the alloy layer material. In someembodiments the minor constituent is about 1% to about 10% of the alloylayer material. In some embodiments the minor constituent is about 1%,about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%,about 9%, or about 10% of the alloy layer material. For example, in theembodiment in FIG. 5A, first layer 244 can be an alloy with a minorconstituent that is about 5% of the alloy layer material, and wherein amajor constituent in about 95% of the alloy layer material. In oneexemplary embodiment first layer 244 is a nickel-boron alloy, whereinthe boron is about 5%, while nickel is about 95%, of alloy layermaterial. In an exemplary embodiment with the structure shown in FIG.5B, first layer 264 is an alloy layer with about 2% boron and about 98%nickel, while third layer 268 is an alloy layer with about 4% boron andabout 96% nickel. The disclosure is obviously not limited to usingnickel as the major constituent or boron as the minor constituent.Additionally, more than 1 minor constituent can be used and can bepresent in a uniform concentration layer.

In embodiments in which the barrier layer has more than one alloy layer(such as in FIG. 5B), each with different concentrations of a minorconstituent, the layer with a lower concentration of the minorconstituent can be disposed adjacent other layers in the connector toprovide added benefits. For example, if there are two layers withdifferent concentrations of boron (but each uniform throughout), thelower boron containing layer can be used for better adhesion for thehigher boron layer above or below it.

In some embodiments the nickel alloy layer (or other metal alloy layer)is a graded layer. That is, one or more components in the alloy layervary in concentration throughout the thickness of the layer. FIG. 6Aillustrates an exemplary alloy layer within a barrier structure (theother layers of the connector are not shown for clarity) in which theconcentration of at least one component varies in the thickness, or “t”,direction. In an exemplary embodiment, layer 282 is a nickel-boron alloywhere nickel is the major constituent and boron in the minor constituent(i.e., nickel is present in a greater percentage than boron). The boronis graded throughout the thickness of layer 282 such that the boronconcentration varies throughout thickness “t” of layer 282. In someembodiments the concentration increases towards the top surface, and insome embodiments the concentration decreases towards the top surface. Insome embodiments the concentration increases from “XT0” to “XT1” frombottom surface “T0” to top surface “T1,” While in some embodiment theconcentration decreases from “XT0” to “XT1” from bottom surface “T0” totop surface “T1.” The variation in concentration can be linear ornon-linear, and the change in concentration need not extend throughoutthe entire thickness of the layer. In an exemplary linear variation, inFIG. 6A the minor constituent (e.g., carbon) varies linearly frombetween 0% and 1% at surface T0 to about 5% at surface T1. In anexemplary non-linear variation, in FIG. 6A the minor constituent (e.g.,boron) varies in a non-linear manner (e.g., exponentially) from surfaceT0 to surface T1. In an alternative embodiment shown in FIG. 6B, alloylayer 286 has a thickness that extends from T0 to T2, but theconcentration of the minor component only varies in concentration fromXT0 to XT1 from T0 to T1, while the concentration of the minor componentis uniform from T1 to T2. Alternatively, the concentration of one ormore components can vary between any two surfaces throughout thethickness of the layer, and can be uniform at any other locationthroughout the thickness of the layer. FIG. 6C illustrates analternative alloy layer in Which the varying concentration section andthe uniform section create an interface that is not parallel with topand bottom surfaces of layer 290. For example, the minor component canvary in concentration from surface T0 to the line connecting points T1and T2, while the concentration can be uniform between T3 and the lineconnecting points T1 and T2.

Any of the alloy layers described herein, including those that aresimply described as part of a laminated barrier layer, can have a gradedalloy layer. For example, in FIG. 5A first layer 244 can be an alloymaterial with major and minor constituents. In an exemplary embodiment,layer 244 is a graded nickel-boron alloy, with the concentration ofboron increasing from the bottom to the top of layer 244, and whereinthe concentration increases from between about 0 and 1% at the bottom toabout 5% at the top of layer 244, Similar graded alloys can be used forlayers 264 and 268 in the embodiment in FIG. 5B.

While nickel is generally referred to herein as a major metalconstituent in the barrier layer, the alloy layer can additionallycomprise other suitable metals such as, for example without limitation,cobalt and tungsten. While boron is typically referred to herein as aminor constituent, any other suitable material may be used, such as, forexample without limitation, carbon, phosphorus, and tungsten. Forexample, in some embodiments the barrier can be anickel-tungsten/nickel/nickel-tungsten barrier layer. Additionally, insome embodiments, the barrier layer can have two or more alloy layers,wherein the alloy layers have different minor constituents. For example,in some embodiments the barrier layer is anickel-boron/nickel/nickel-tungsten barrier layer.

In embodiments in which at least one barrier layer is graded, the changein percent of the minor constituent from a first location in the layerto a second location in the layer can be from about 0 to about 49%. Insome embodiments the grade is from about 0% to about 10%. In someembodiments it is from about 0% to about 9%, from about 0% to about 8%,from about 0% to about 7%, from about 0% to about 6%, from about 0% toabout 5%, from about 0% to about 4%, from about 0% to about 3%, fromabout 0% to about 2%, or from about 0% to about 1%. These exemplarychanges in percentage are not intended to be limiting and otherpercentages can be used. For example, a boron concentration could varyfrom about 10% to about 30% throughout a thickness of the layer.

In alternative embodiments in which there are more than one alloy layerin the barrier layer, one of the layers can have a uniform concentrationof a minor constituent while a second layer has a varying concentrationof the same or a different minor constituent. For example, in theembodiment in FIG. 5B, first layer 264 can be an alloy and have auniform concentration of a minor constituent throughout, while thirdlayer 268 can have a graded concentration of the same or different minorconstituent. In one exemplary embodiment shown in FIG. 5B, layer 264 isa nickel-boron alloy with 5% boron, while layer 268 is a boron-nickelalloy whose boron concentration varies from about 1% at the bottom ofthe layer to about 5% at the top of the layer.

In some embodiments the thickness of the total barrier layer is about0.01 to about 1.5 microns, compared to traditional barrier layers whosethickness can be about 1.5 microns to about 5 microns or more. That is,in exemplary embodiments in FIGS. 4A-5B, overall barrier structures 210,225, 247, and 272, respectively, can be about 0.01 microns to about 1.5microns in thickness. In some embodiments a discrete layer within thebarrier that is a non-alloy layer (e.g., a nickel layer) is about 5 nmto about 200 nm thick, and in some embodiments is about 5 nm to about 50nm thick. For example, in the embodiment in FIG. 4A, first layer 204 canbe a nickel layer flash deposited on substrate 202, and is about 5 nm toabout 50 nm thick. In embodiments in which there are more than onenon-alloy layer, each of those layers can be about 5 nm to about 50 nmthick. For example, in the embodiment in FIG. 4B, each of layers 224 and228 within barrier layer 225 can be about 5 nm to about 50 nm.

In some embodiments the alloy barrier layers are between about 30 nmthick and about 800 nm thick. In some embodiments an individual alloylayer is between about 100 nm and about 700 nm thick. In someembodiments they are between about 200 nm and about 600 nm thick. Insome embodiments the alloy layer is between about 300 nm and about 500nm thick. In an exemplary embodiment an alloy layer is about 400 nmthick, such as in layer 156 in the embodiment in FIG. 11A describedbelow. In some embodiments the alloy barrier layers are about 20 nm toabout 200 nm thick.

In a merely exemplary embodiment of the structure disclosed in FIG. 5B,layer 264 is between about 20 nm and 200 nm, layer 266 is between about5 nm and about 50 nm, and layer 268 is between about 20 nm and about 200nm. The total thickness of layer 272 is between about 45 nm and about450 nm.

The disclosure also includes methods of preparing an electricalconnection, including the barrier layers described herein. FIGS. 7A and7B illustrate an exemplary method of preparing an electrical connectionwith a barrier layer that comprises a graded alloy layer. In FIG. 7A,substrate 74 has been deposited in dielectric 72. Passivation layer 76and polymer 78 are then deposited. Polymer 78 is then lithographicallypatterned, polymer 78 is cured, and. portions of passivation layer 76are removed by REF methods to expose substrate 74 beneath, as shown inFIG. 7A. In FIG. 7B, graded alloy layer 80 (e.g., a graded NiB layer) isselectively coated over exposed substrate 74. Conductive material 82 isthen coated over graded alloy layer 80. Conductive material 82 can beimmersion coated on alloy layer 80. The connector can be used in myriadelectrical applications.

Exemplary methods of depositing a barrier layer (either discrete layersor the entire barrier layer) with a uniform concentration of a minorconstituent can be found in U.S. Pat. No. 7,521,128, the disclosure ofwhich is incorporated by reference.

In some embodiments the graded alloy layer is formed by electrolyticplating. The electroplating current density can range from about 5mA/cm² to about 200 mA/cm², but in some exemplary embodiments it isbetween about 20 and about 100 mA/cm², while in some embodiments it isabout 50 mA/cm². The current density can be modulated to control theconcentration of a first minor constituent within the barrier layer. Insome embodiments nitrogen and oxygen are bubbled into the solutionduring the plating process to control the gradient within the barrierlayer. For higher levels of a minor constituent (e.g., boron), theamount of nitrogen that is bubbled into the plating solution isincreased, while for higher levels of a major constituent (e.g.,nickel), the amount of oxygen that is bubbled into solution isincreased. By varying the concentration of nitrogen and oxygen bubbledinto solution the gradient of the alloy can be controlled during theplating process. Electroless plating processes can also be used to platea graded alloy barrier layer.

FIGS. 8A-8C illustrate an exemplary method of producing a wire bond thatincorporates one or more barrier layers within. In FIG. 8A, polymer 108has been lithographically patterned, cured, and a portion of passivationlayer 106 has been removed by REF methods to expose substrate 104beneath. Next as shown in FIG. 8B, barrier layer 110 is globally coatedover polymer 108 and substrate 104. Barrier layer 110 can be any of thebarrier layers described herein, such as a laminated barrier layer, agraded barrier layer, or any combination thereof. In an exemplaryembodiment, barrier layer 110 is a nickel-boron alloy. Next, in Step 8C,barrier layer 110 is patterned to remove unwanted barrier layermaterial. The substrate may be annealed to reduce resistivity.Conductive layer 112, such as a gold layer or a gold alloy layer, isthen selectively deposited on barrier layer 110. Conductive layer 112can be deposited by immersion deposition. A wire can then be bonded tothe wire bond pad as shown in FIG. 8C.

FIGS. 9A-9D illustrate an exemplary method of manufacturing and use ofany of the barrier layers herein in a solderable structure. In FIG. 9A,barrier layer 130 is coated as three discrete layers, such as in theembodiment in FIG. 4B. For example, barrier layer 130 can be aNi/Ni-alloy/Ni barrier layer. Next, resist material 132 is coated andpatterned, as shown in FIG. 9B. In FIG. 9C, solderable material isthru-mask plated on barrier layer 130. In this embodiment the conductivelayer is the solderable material. In FIG. 9D, resist 132 is stripped andunwanted portions of barrier layer 130 are removed, exposing solderablematerial 134. In some embodiments conductive material can be screenprinted into the cavities in the resist. In other embodiments, moltensolder may be filled into the gaps.

In FIGS. 10A and 10B, barrier layer 144 has been disposed on substrate142. Barrier layer 144 can be any barrier layer described herein, suchas a laminated barrier layer, with at least one layer being an alloylayer with a uniform concentration of a minor constituent. In FIG. 10B,conductive layer 146 has been coated on barrier layer 146. In anexemplary embodiment, gold is the conductive layer that is coated over abarrier layer with at least one layer that is nickel-boron with avarying concentration of boron throughout at least a portion of thealloy layer.

FIG. 11A shows a scanning electron microscope (“SEM”) section of aportion of an electrical connector including substrate 152, firstbarrier layer 154, and second barrier layer 156, as deposited. In thisembodiment, substrate 152 is a layer of copper, first barrier layer 154is a flash layer of nickel, while second layer 156 is a nickel-boronalloy layer with the boron being uniformly distributed throughout secondlayer 156. As set forth above, boron generally provides better corrosionresistance for the substrate, but higher boron concentrations can causethe connector to be brittle and undesirably crack more easily. Thenickel layer 154, immediately adjacent substrate 152, does not containboron, which helps prevent the connection from cracking. While the flashlayer of nickel can help minimize the risk of cracking, it need not bepresent and in some applications may not be needed or even helpful. Inthe embodiment in FIG. 11A, the thicknesses as measured using SEM areabout 412 nm for layer 156, about 50-100 nm for layer 154, and about 575nm for layer 152. FIG. 11B shows a SEM section of the section from FIG.11A after 10 reflow cycles at 300° C. Layer 156 is about 475 nm thick,layer 154 is between about 50 nm and 100 nm thick, and layer 152 isabout 470 nm thick.

FIG. 12 shows a SEM section of a portion of an exemplary connectionafter 10 reflows cycle at 300° C. including substrate 172 and barrierlayer 174. Barrier layer 174 is a nickel-boron alloy with a uniformconcentration of boron throughout. Layer 174 is about 465 mn thick andlayer 172 is about 470 nm thick. In FIG. 12, the copper substrate grainsize is larger than the grain size of the copper in the embodiment inFIG. 11A.

The embodiments in FIGS. 11A, 11B, and 12 are illustrative only and theactual thicknesses may vary. For example, in many applications barrierlayer 156 would be thinner than shown. In some embodiments layer 156would be less than half of the thickness shown, and could be about ⅙ ofthe thickness shown.

Any of the barrier layers described herein can be incorporated into thedevices described in U.S. Pub. No. 2009/0065907, filed Jul. 31, 2008,the disclosure of which is incorporated herein by reference.

Additionally, the barrier layers described herein can be used in placeof or in addition to, any of the barrier layers described in U.S. PatentApplication No. 13/______, entitled “Connector Structures and Methods,”attorney docket number 704.200, filed on the same day as the instantapplication, the disclosure of which is incorporated by referenceherein.

Another merely exemplary use of the barrier layers described herein isin a light emitting diode (“LED”), such as in the semiconductor die of aLED. The barrier layers herein can be used as a barrier between, forexample, an aluminum layer and a copper layer.

While preferred embodiments of the present disclosure have been shownand. described herein, it will be obvious to those skilled in the artthat such embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the disclosure. It should beunderstood that various alternatives to the embodiments of thedisclosure described herein may be employed in practicing theembodiments in the disclosure.

1. A device comprising an electrical connection structure comprising: aconductive substrate; a variable-composition nickel alloy layer abovethe conductive substrate and in electrical contact with the conductivesubstrate, the variable-composition nickel alloy layer having a bottomsurface overlying and physically contacting a first surface of a firstmaterial, and having a top surface underlying and physically contactinga second surface of a second material, wherein the first and secondmaterials do not have nickel as a major constituent, thevariable-composition nickel alloy layer comprising a minor constituentselected from a group consisting of boron, carbon, and tungsten, whereinat least over a portion of the conductive substrate, the concentrationof the minor constituent varies throughout the variable-compositionnickel alloy layer in a direction from the bottom surface of thevariable-composition nickel alloy layer to the top surface of thevariable-composition nickel alloy layer; and a conductive layer disposedabove the variable-composition nickel alloy layer and in electricalcontact with the variable-composition nickel alloy layer and theconductive substrate.
 2. The device of claim 1 wherein the first surfaceis a top surface of the conductive substrate.
 3. The device of claim 1wherein the first material comprises at least one of gold, silver,palladium, platinum, copper.
 4. The device of claim 1 wherein the secondsurface is a bottom surface of the conductive layer.
 5. The device ofclaim 1 wherein the second material comprises at least one of gold,silver, palladium, platinum, copper.
 6. The device of claim 1 whereinthe conductive layer is solder.
 7. The device of claim 1 wherein atleast over said portion of the conductive substrate, the concentrationof the minor constituent in the variable-composition nickel alloy layeris at most 10% by weight.
 8. The device of claim 1 wherein at least oversaid portion of the conductive substrate, the nickel concentration inthe variable-composition nickel alloy layer is at least 80% by weight.9. The device of claim 1 wherein the minor constituent is boron.
 10. Thedevice of claim 1 wherein the minor constituent is carbon.
 11. Thedevice of claim 1 wherein the minor constituent is tungsten.
 12. Thedevice of claim 1 wherein a top surface of the conductive layer isavailable for being bonded to a wire external to the device.
 13. Thedevice of claim 1 further comprising a wire bonded to a top surface ofthe conductive layer.
 14. A device comprising an electrical connectionstructure comprising: a conductive substrate whose top surface does notinclude nickel as a major constituent; a variable-composition nickelalloy layer on the conductive substrate, the variable-composition nickelalloy layer comprising a minor constituent selected from a groupconsisting of boron, carbon, and tungsten, wherein at least over aportion of the conductive substrate, the concentration of the minorconstituent varies throughout the variable-composition nickel alloylayer in a direction from the bottom surface of the variable-compositionnickel alloy layer to the top surface of the variable-composition nickelalloy layer; and a conductive layer on the variable-composition nickelalloy layer, the conductive layer aving a bottom surface which does notinclude nickel as a major constituent.
 15. The device of claim 14wherein the conductive substrate is gold, silver, palladium, platinum,or copper.
 16. The device of claim 14 wherein the conductive layer isgold, silver, palladium, platinum, or copper.
 18. The device of claim 14wherein the conductive layer is solder.
 19. The device of claim 14wherein the minor constituent is boron.
 20. The device of claim 14wherein the or constituent is carbon or tungsten.